TWI460310B - A titanium-based metal, a tungsten-based metal, a titanium-tungsten-based metal, or an etching solution of these nitrides - Google Patents
A titanium-based metal, a tungsten-based metal, a titanium-tungsten-based metal, or an etching solution of these nitrides Download PDFInfo
- Publication number
- TWI460310B TWI460310B TW098128864A TW98128864A TWI460310B TW I460310 B TWI460310 B TW I460310B TW 098128864 A TW098128864 A TW 098128864A TW 98128864 A TW98128864 A TW 98128864A TW I460310 B TWI460310 B TW I460310B
- Authority
- TW
- Taiwan
- Prior art keywords
- based metal
- titanium
- tungsten
- etching
- nitride
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 180
- 239000002184 metal Substances 0.000 title claims description 180
- 238000005530 etching Methods 0.000 title claims description 153
- 239000010936 titanium Substances 0.000 title claims description 98
- 229910052719 titanium Inorganic materials 0.000 title claims description 85
- 229910052721 tungsten Inorganic materials 0.000 title claims description 81
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 73
- 239000010937 tungsten Substances 0.000 title claims description 70
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims description 69
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 title claims description 51
- 150000004767 nitrides Chemical class 0.000 title claims description 33
- 239000007788 liquid Substances 0.000 claims description 57
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 56
- -1 organic acid salt Chemical class 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 5
- 239000001393 triammonium citrate Substances 0.000 claims description 5
- 235000011046 triammonium citrate Nutrition 0.000 claims description 5
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- 229940090948 ammonium benzoate Drugs 0.000 claims 1
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 claims 1
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims 1
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 1
- WVBBLATZSOLERT-UHFFFAOYSA-N gold tungsten Chemical compound [W].[Au] WVBBLATZSOLERT-UHFFFAOYSA-N 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 235000010235 potassium benzoate Nutrition 0.000 claims 1
- 239000004300 potassium benzoate Substances 0.000 claims 1
- 229940103091 potassium benzoate Drugs 0.000 claims 1
- 239000001508 potassium citrate Substances 0.000 claims 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims 1
- 235000010234 sodium benzoate Nutrition 0.000 claims 1
- 239000004299 sodium benzoate Substances 0.000 claims 1
- 239000001509 sodium citrate Substances 0.000 claims 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims 1
- 229940039790 sodium oxalate Drugs 0.000 claims 1
- 235000015870 tripotassium citrate Nutrition 0.000 claims 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims 1
- 229940038773 trisodium citrate Drugs 0.000 claims 1
- 239000010408 film Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000758 substrate Substances 0.000 description 17
- 150000002739 metals Chemical class 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 13
- 238000005187 foaming Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229910001080 W alloy Inorganic materials 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910000484 niobium oxide Inorganic materials 0.000 description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- GXEKYRXVRROBEV-FBXFSONDSA-N (1r,2s,3r,4s)-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid Chemical compound C1C[C@@H]2[C@@H](C(O)=O)[C@@H](C(=O)O)[C@H]1O2 GXEKYRXVRROBEV-FBXFSONDSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- USZAQQBEAQJLMT-UHFFFAOYSA-N 2-hydroxy-2-methylbutanedioic acid;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)C(O)(C)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O USZAQQBEAQJLMT-UHFFFAOYSA-N 0.000 description 1
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- IAOQICOCWPKKMH-UHFFFAOYSA-N dithieno[3,2-a:3',2'-d]thiophene Chemical group C1=CSC2=C1C(C=CS1)=C1S2 IAOQICOCWPKKMH-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- MWRJCEDXZKNABM-UHFFFAOYSA-N germanium tungsten Chemical compound [Ge].[W] MWRJCEDXZKNABM-UHFFFAOYSA-N 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Description
本發明有關鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液。本發明尤其有關相對於鈦系金屬、鎢系金屬、鈦鎢系金屬以外之金屬之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物之選擇蝕刻性優異之蝕刻液。
屬於鈦系金屬的金屬鈦(Ti)、氮化鈦(TiN)或鈦合金已被使用作為半導體裝置、液晶顯示器、MEMS(微電子機械系統)裝置、印刷電路基板等之貴金屬或鋁(Al)、銅(Cu)電路之底層、覆蓋層。又,亦被使用於半導體裝置中作為阻障金屬、閘極金屬。
一般的鈦系金屬的蝕刻,已知有利用氫氟酸/硝酸混合液、過氧化氫/氫氟酸混合液進行處理之方法,但由於該等含有氫氟酸故有亦會侵蝕矽基板或玻璃基板之缺點。又,亦有將裝置中存在的Al電路等耐腐蝕性較弱金屬也同時蝕刻掉的問題。
為了改善該等液體的缺點,已揭示有過氧化氫/氨/EDTA(乙二胺四乙酸)混合液以及過氧化氫/磷酸鹽混合液(專利文獻1、2)。然而,該等對鈦系金屬的蝕刻速率小且過氧化氫的分解迅速而無法安定地蝕刻,故作為改良該等液體者,已提案有由過氧化氫/磷酸/氨混合液所構成之蝕刻液(專利文獻3)。然而,此蝕刻液雖改善了蝕刻速率但蝕刻液卻會激烈發泡,故會在基板表面上附著氣泡,而有附著氣泡之部分無法進行蝕刻之缺點。又,亦有因過氧化氫發泡、分解導致蝕刻速率的降低變大的問題。該混合物雖已以氨調整至指定的pH後使用,但以pH的少許差異改變蝕刻速率及發泡狀態,亦有蝕刻條件的安定性方面的問題。
另一方面,作為含有過氧化氫之洗淨液已揭示有於過氧化氫/氨/水中包含有機酸銨鹽之半導體洗淨液(專利文獻4)。然而,該半導體洗淨液為使於半導體製造步驟中去除基板上所附著之微粒子等之污染物之洗淨液,雖記載有使摻雜氧化膜與非摻雜氧化膜之蝕刻速率較小,但有關鈦系金屬之蝕刻全然未記載。又,專利文獻5中,揭示含有過氧化氫/羧酸鹽/水之光阻劑殘渣剝離用組成物。此組成物目的係用以剝離光阻劑灰化後之光阻劑殘渣,非以鈦系金屬之蝕刻作為對象。
又,鎢或鎢合金已使用於液晶顯示器、半導體裝置之薄膜電晶體之閘極、電路、障壁層或接觸孔、貫通孔(via hole)之埋入。且於MEMS(微機電系統)領域中,亦已利用作為鎢加熱器。
鎢或鎢合金大多藉CVD或濺鍍法予以成膜。但以該等方法成膜之際,亦會附著於半導體裝置在其實際的元件形成部以外之基板(晶圓)背面、基板(晶圓)邊緣、成膜裝置外壁、排氣管內等,而有其等剝離且於元件形成部發生異物之問題。作為其對策之一,有利用蝕刻液去除不需要的膜。此異物對策以外,亦期望於半導體裝置、液晶顯示裝置、MEMS裝置之製造步驟中,以比乾蝕刻生產性更優異的濕蝕刻對鎢或鎢合金進行加工。尤其於不要求如半導體裝置程度的加工精度之液晶顯示器、MEMS裝置則適用濕蝕刻法。
作為鎢系金屬的蝕刻液、去除液,廣泛已知有氟化氫酸與硝酸之混合液(非專利文獻1等),但該等由於亦會溶解矽基板或二氧化矽膜、玻璃基板而不佳。又,亦有同時蝕刻裝置中所存在之Al電路等耐蝕性弱之金屬的問題。另一方面,以過氧化氫水為主成分之蝕刻液已見於例如專利文獻6~9等,於專利文獻9中已詳述歸納以往過氧化氫為主的蝕刻液的問題點。據此記載有蝕刻速度變慢、伴隨著鎢溶解pH產生變動的結果,蝕刻速率變動使蝕刻選擇性惡化。再者,亦記載有若鎢被溶解則過氧化氫的分解速度將大幅增大。作為解決該等問題者雖已公開於過氧化氫中添加唑(專利文獻8),但過氧化氫之分解抑制尚不足,蝕刻速率並不穩定。如上述,以過氧化氫水作為主要成分的蝕刻液,於現狀中實用上尚未具鎢的蝕刻速率安定、鎢的蝕刻選擇性大、液體壽命長者。
專利文獻1:特開平08-013166號公報
專利文獻2:特開2000-311891號公報
專利文獻3:特開2005-146358號公報
專利文獻4:特開平10-284452號公報
專利文獻5:特開2005-183525號公報
專利文獻6:特開昭62-143422號公報
專利文獻7:特開平8-250462號公報
專利文獻8:特開2002-53984號公報
專利文獻9:特開2004-31791號公報
非專利文獻1:監修坂本正典、發行者島健太郎「半導體製造製程材料及化學品」,2006年9月30日發行第一版,第144頁。
本發明係消除如上述之問題點者,而提供可藉由減少蝕刻時之蝕刻液發泡而減低蝕刻對象物之不均一蝕刻,且蝕刻速率安定之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液。再者,可提供不腐蝕基板而對於鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物之蝕刻選擇性優於鈦系金屬、鎢系金屬、鈦鎢系金屬以外的金屬之蝕刻液。
本發明人等為解決上述課題而重複積極研究之結果,發現若使用含有過氧化氫及有機酸鹽之水溶液,則可減少蝕刻液之發泡且可以減低蝕刻對象物之不均一蝕刻且蝕刻速率安定。且發現若使用本發明之蝕刻液,並不會蝕刻鎳、銅、鋁等之其他金屬或基板材料(玻璃、矽、氧化矽、氮化矽),而可選擇性地蝕刻鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物,因而完成本發明。
亦即,本發明包含下列所述者。
[1]一種鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其特徵為包含10~40質量%之過氧化氫、0.1~15質量%之有機酸鹽及水。
[2]一種鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其特徵為僅由10~40質量%之過氧化氫、0.1~15質量%之有機酸鹽及水所構成。
[3]如[1]所述之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其進而包含0.005~4.5質量%之氨。
[4]如[1]至[3]中任一項所述之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中上述有機酸鹽為選自檸檬酸、甲酸、草酸、乙酸、酒石酸、苯甲酸及琥珀酸之銨鹽之至少一種。
[5]如[4]所述之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中上述有機酸之銨鹽為選自檸檬酸氫二銨、檸檬酸三銨、草酸銨、甲酸銨、乙酸銨之至少一種。
[6]如[1]至[5]中任一項所述之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中鈦系金屬或其氮化物相對於Al、Ni、Cu、Cr、Ru、Ta、Si或以該等元素作為主成分之合金之蝕刻速率比為20以上。
[7]如[1]至[5]中任一項所述之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中鈦系金屬或其氮化物相對於玻璃、矽、氧化矽或氮化矽之蝕刻速率比為20以上。
[8]一種電子裝置之製造方法,該方法具有藉由[1]至[7]中任一項所述之蝕刻液蝕刻鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物之步驟。
本發明之蝕刻液,由於對鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物之選擇蝕刻性比對鈦系金屬、鎢系金屬、鈦鎢系金屬以外之金屬或基板材料(玻璃、矽、氧化矽)之蝕刻選擇性優異,且發泡較少,故使用本發明之蝕刻液可對鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物進行均一地蝕刻。
以下詳細說明本發明。
本發明之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液係由含有過氧化氫及有機酸鹽類之水溶液所構成。
過氧化氫在蝕刻液中含有10~40質量%,更好為15~35質量%,又更好為20~35質量%。過氧化氫之濃度低於10質量%時,鈦或鎢、鈦鎢合金之蝕刻速率變低而不實用。另一方面,當過氧化氫之濃度高於40質量%時,過氧化氫之分解變多而不實用。
本發明中可用的有機酸鹽並無特別限制,但在不需要金屬雜質之半導體等電子裝置之製造步驟中使用有機酸鹽時,更好使用銨鹽。
有機酸鹽在蝕刻液中含有0.1~15質量%,更好為含有1~10質量%,又更好為含有3~8質量%。有機酸鹽之濃度低於0.1質量%時,蝕刻速率變低,而不實用。另外,即使該濃度高過15質量%時,蝕刻速率亦無法大幅提升。
至於有機酸鹽並無特別限制,可舉例為檸檬酸、甲酸、草酸、乙酸、酒石酸、琥珀酸、蘋果酸、馬來酸、丙二酸、戊二酸、己二酸、D-聚葡萄糖酸、衣康酸、檸康酸、中康酸、2-氧代戊二酸、偏苯三酸、菌多酸(endothal)、谷胺酸、甲基琥珀酸、檸蘋酸(Citramalic acid)等之鹽。本發明者針對鈦系金屬、鎢系金屬或該等之氮化物評價蝕刻特性之結果,發現蝕刻液係中性比酸性可獲得高的蝕刻速率之傾向。因而使用有機酸鹽。較好為使用檸檬酸、甲酸、草酸、乙酸、酒石酸、琥珀酸之鹽,更好為使用檸檬酸氫二銨、檸檬酸三銨、草酸銨、甲酸銨、乙酸銨。該等可單獨使用,亦可組合兩種以上使用。另外,有機酸銨鹽可作為有機酸銨鹽本身使用,亦可在蝕刻液中使有機酸與氨反應使用,並沒有任何限制。
為提高鈦系金屬、鎢系金屬、鈦鎢系金屬或此等之氮化物的蝕刻速率可依據需要添加氨。添加氨時,蝕刻液中之濃度為0.005~4.5質量%,更好為0.05~2質量%,又更好為0.1~0.5質量%之範圍。氨之濃度高於4.5質量%時,可提昇鈦系金屬、鎢系金屬或此等之氮化物的蝕刻速率,但裝置中存在之Al等容易被鹼腐蝕的金屬被蝕刻而不佳。
由於上述組成之本發明蝕刻液對鈦系金屬、鎢系金屬、鈦鎢系金屬或此等之氮化物蝕刻時發泡少,因此可進行均勻蝕刻。另外,本發明之蝕刻液對鈦系金屬、鎢系金屬、鈦鎢系金屬以外之金屬或基板材料(玻璃、矽、氧化矽、氮化矽)之蝕刻速率小,相對於此鈦系金屬、鎢系金屬、鈦鎢系金屬或此等之氮化物之選擇蝕刻性(鈦系金屬、鎢系金屬或此等之氮化物之蝕刻速率相對於鈦系金屬、鎢系金屬以外之金屬或基板材料(玻璃、矽、氧化矽、氮化矽)之蝕刻速率之比)為20以上為佳。又,本發明之蝕刻液在不影響蝕刻特性之範圍內亦可添加上述以外之各種成分,例如潤濕劑、界面活性劑、著色劑、抗發泡劑、有機溶劑等。
本說明書中所謂的鈦系金屬,除金屬鈦(Ti)以外,意指含有鈦作為主成分(70質量%以上)之合金。又,所謂鈦系金屬之氮化物意指金屬鈦或鈦合金之氮化物,典型之例舉例為氮化鈦。鈦合金之具體例舉例為矽化鈦(TiSi)。同樣的所謂鎢系金屬,除金屬鎢(W)以外,意指含有鎢作為主成分(70質量%以上)之合金。又,所謂鎢系金屬之氮化物意指金屬鎢或鎢合金之氮化物。典型之例舉例為氮化鎢。鎢合金之具體例舉例為鎢化鉬(MoW)、矽化鎢(WSi)等。
又,本說明書中,所謂鈦鎢系金屬意指包含鈦與鎢二者,且二者之合計為70質量%以上之合金。另外,鈦鎢系金屬之氮化物意指該等鈦鎢系合金之氮化物。
對該等鈦系金屬、鎢系金屬、鈦鎢系金屬於基板上之成膜方法並無特別限制,可使用CVD、濺鍍、蒸鍍法之任一種方法,又成膜條件亦無限制。且,本說明書中所謂的鈦系金屬、鎢系金屬、鈦鎢系金屬以外之金屬係指Al、Ni、Cu、Cr、Ru、Ta、Si或以該等元素之任一種作為主成分(70質量%以上)(包含複數元素時其合計量為70質量%以上)之合金,亦包含具有其他元素者。
使用上述鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物之裝置並無特別限制,可使用於全部電子裝置中。該等電子裝置舉例為液晶顯示器、半導體裝置、MENS裝置、印刷電路基板、有機EL顯示器、場發射顯示器、電子紙、電漿顯示器等。本發明所謂的蝕刻意指利用蝕刻顯像之全部者,且當然包含將鈦系金屬、鎢系金屬、鈦鎢系金屬圖型化者,亦包含洗淨去除鈦系金屬或鎢系金屬、鈦鎢系金屬之殘留物等之用途。亦包含於最終製品中雖未殘留鈦或鎢、鈦鎢合金,但在製造製程過程中使用鈦系金屬或鎢系金屬、鈦鎢系金屬,使鈦系金屬或鎢系金屬、鈦鎢系金屬全部溶解於蝕刻液中而去除者。
以本發明之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液處理,通常係藉由浸漬法進行,但其他方法亦可以例如噴佈法、旋轉蝕刻法等處理。以浸漬法處理之條件係依據過氧化氫濃度、有機酸銨鹽之種類或含量、鈦系金屬、鎢系金屬、鈦鎢系金屬或此等之氮化物之膜厚等而不同,無法概略規定,但一般的處理溫度為20~80℃,更好為30~60℃。該等處理可邊施加超音波邊進行。
以下列舉實施例及比較例具體說明本發明,但本發明並不受下列敘述限制。
以濺鍍設備將Ti、W及Al分別成膜(膜厚各為50nm)於LCD(液晶顯示器)用無鹼玻璃基板上之貼附Ti、W及Al膜之樣品基板,切成約0.5cm見方,獲得樣品片。於100毫升燒杯中注入20毫升下表1所示之各實施例及比較例之組成之蝕刻液,且加熱至50℃。將上述貼附Ti、W、Al膜之樣品片各一片同時投入該蝕刻液中,且以目視觀察各濺鍍膜全部消失之時間。由進行同樣測定3次之結果分別計算出Ti、W及Al之蝕刻速率之平均值。表1中彙整顯示各實施例、比較例之蝕刻速率。表1中所示之各蝕刻液之構成成份以外為水(超純水)。又,各實施例及比較例之蝕刻液係KISHIDA化學製特級品之35質量%之過氧化氫水,關東化學製造之EL級之28質量%之氨水,使用市售有機酸銨依據需要以超純水調製成各組成。
除以Ni、Cu、Cr、Ru、Ta、Si替代Ti、W及Al成為濺鍍膜之材質以外,餘與上述Ti、W、Al之蝕刻速率之測定相同,使用貼附Ni、Cu、Cr、Ru、Ta、Si膜之樣品片進行測定,計算出蝕刻速率。下表2中顯示使用實施例1、2、3之組成之蝕刻液測定之結果。
於100毫升之燒杯中注入20毫升表1之實施例1之組成之蝕刻液,且加熱至50℃。將一片貼附Ti膜之樣品片投入維持於50℃之蝕刻液中。以該樣品片投入時作為起始點(0時),隨後一邊維持在50℃之溫度一邊每一小時投入一片貼附Ti膜之樣品片,且測定至6小時後之蝕刻速率。另外,蝕刻速率之測定方法與前述之方法相同。比較例使用過氧化氫30質量%、磷酸0.3質量%,氨0.02質量%,超純水69.68質量%之蝕刻液(比較例3),進行同樣之試驗。其結果示於圖1中。
準備表1之實施例1組成之蝕刻液,維持在恆溫50℃下。將切成0.5cm見方之貼附Ti膜(厚度50nm)之樣品片浸漬於該蝕刻液中一分鐘。以照相攝影自此時液體之發泡狀態。又,至於比較例,使用過氧化氫30質量%、磷酸0.3質量%,氨0.02質量%,超純水69.68質量%之蝕刻液(比較例3),同樣的評估發泡狀態。結果示於圖2、3中。
於50毫升之燒杯中注入20毫升表1之實施例12之組成之蝕刻液,且加熱至45℃。將一片貼附TiW膜之矽晶圓片(約0.5cm見方,W膜厚200nm)投入維持於45℃之蝕刻液中。以該樣品片投入時作為起始點(0時),隨後一邊維持在45℃之溫度下一邊每6小時投入一片貼附TiW膜之樣品片,且測定至66小時後之蝕刻速率。又,蝕刻速率之測定方法與前述之方法相同。作為比較例,使用過氧化氫30質量%、超純水70質量%之蝕刻液(比較例2),進行同樣之試驗。其結果示於圖4。又,TiW之組成係使用包含10質量%之Ti、90質量%之W者。
表1中所示之全部實施例1~26組成之蝕刻液,Ti、W之蝕刻速率相對於Al之蝕刻速率之比為20以上,Ti、W之選擇蝕刻性優異。蝕刻速率於一部份組成Ti之蝕刻速度有些小但大致上也大於50nm/min而為良好。另一方面,W之蝕刻速度均為150nm/min以上而為良好。相對於此,比較例1之蝕刻液於Ti、W之蝕刻速率均小如50nm/min以下而不充分。比較例2中Ti之蝕刻速率小如50nm/min以下而不充分。
又,由表2可了解本發明之蝕刻液,與Al相同,對Ni、Cu、Cr、Ru、Ta、Si、SiO2
、Si3
N4
之蝕刻速率亦小,相對於此等,對鈦、鎢具有良好的選擇蝕刻性。再者,由圖1可了解本發明之蝕刻液對鈦之蝕刻速率之經時下降率小,為安定性優異。相對於此,比較例3之蝕刻液其初期之Ti蝕刻速率(150nm/min)雖然高於實施例1之蝕刻液,但蝕刻速率經時變化(下降)大,安定性差。
再者,針對WN、TiW、TiN以實施例1之組成同樣測定蝕刻速率,分別為320nm/min、200nm/min、120nm/min。至於此處之TiW之組成係使用Ti、W分別為10質量%、90質量%者。WN、TiN使用如化學式之組成者。
圖2、3顯示將貼附Ti膜之樣品片投入蝕刻液中該時之蝕刻液發泡狀態。相片為自上方觀察燒杯之照片。於圖3(比較例3之蝕刻液)發現蝕刻液有相當的發泡,相對地,於圖2(實施例1之蝕刻液)中幾乎未觀察到發泡。據此可知由於本發明之蝕刻液在蝕刻時之氣泡產生少,因此對鈦系金屬之均勻蝕刻有利。
由圖4可了解本發明之蝕刻液之TiW蝕刻速率經時下降率小,安定性優異。相對於此,比較例2之蝕刻液之TiW蝕刻速率(50nm/min)之經時變化(下降)大,安定性差。
藉由使用本發明之蝕刻液可均勻的蝕刻鈦、鎢及其合金或者其氮化物。又,本發明之蝕刻液由於對銅、鎳、鋁等其他金屬或玻璃、矽、氧化矽膜之蝕刻速率小,因此不會損及基板、甚至氧化矽膜,因此可用於半導體裝置、液晶顯示器等電子裝置之製造。
圖1為表示實施例1及比較例3之組成的蝕刻液對鈦之蝕刻速率經時變化之圖。
圖2為表示附有Ti膜之樣品片浸漬於實施例1之蝕刻液時之發泡狀態。
圖3為表示附有Ti膜之樣品片浸漬於比較例3之蝕刻液時之發泡狀態。
圖4為顯示以實施例12及比較例2之組成的蝕刻液對鈦鎢(TiW)之蝕刻速率經時變化之圖。
Claims (13)
- 一種鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其特徵為包含10~40質量%之過氧化氫、0.1~5質量%之有機酸鹽及水,其中有機酸鹽為選自檸檬酸三銨、甲酸銨、草酸銨、酒石酸銨、苯甲酸銨、琥珀酸銨、檸檬酸氫二銨、檸檬酸三鉀、檸檬酸三鈉、草酸鈉、苯甲酸鉀、苯甲酸鈉之至少一種。
- 一種鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其特徵為僅由10~40質量%之過氧化氫、0.1~15質量%之有機酸鹽及水所構成。
- 如申請專利範圍第2項之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中有機酸鹽為0.1~5質量%。
- 如申請專利範圍第1項之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其進而包含0.005~4.5質量%之氨,其中上述有機酸鹽為選自檸檬酸、甲酸、草酸、酒石酸、苯甲酸及琥珀酸之銨鹽之至少一種。
- 如申請專利範圍第1至3項中任一項之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中上述有機酸鹽為選自檸檬酸、甲酸、草酸、酒石酸、苯甲酸及琥珀酸之銨鹽之至少一種。
- 如申請專利範圍第5項之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中上述有機酸之 銨鹽為選自檸檬酸氫二銨、檸檬酸三銨、草酸銨、甲酸銨、之至少一種。
- 如申請專利範圍第1至3項中任一項之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中鈦系金屬或其氮化物相對於Al、Ni、Cu、Cr、Ru、Ta、Si或以該等元素作為主成分之合金之蝕刻速率比為20以上。
- 如申請專利範圍第1至3項中任一項之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中鈦系金屬或其氮化物相對於玻璃、矽、氧化矽或氮化矽之蝕刻速率比為20以上。
- 一種電子裝置之製造方法,其特徵為該方法具有藉由申請專利範圍第1至8項中任一項之蝕刻液蝕刻鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物之步驟。
- 如申請專利範圍第3項之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中,該有機酸鹽為檸檬酸鹽。
- 如申請專利範圍第1項之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中,該有機酸鹽為選自檸檬酸氫二銨、檸檬酸三銨之至少一種。
- 如申請專利範圍第10項之鈦系金屬、鎢系金屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中,該有機酸鹽為選自檸檬酸之銨鹽。
- 如申請專利範圍第12項之鈦系金屬、鎢系金 屬、鈦鎢系金屬或該等之氮化物的蝕刻液,其中,該檸檬酸之銨鹽為選自檸檬酸氫二銨、檸檬酸三銨之至少一種。
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KR20210115794A (ko) | 2020-03-16 | 2021-09-27 | 동우 화인켐 주식회사 | 코발트막 식각 조성물 |
CN116180059B (zh) * | 2023-04-28 | 2024-03-19 | 中国电子科技集团公司第十四研究所 | 一种htcc基板化学镀挂具及使用其进行化学镀的方法 |
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- 2009-08-25 EP EP09813013.1A patent/EP2322692B1/en active Active
- 2009-08-25 CN CN2009801350620A patent/CN102149851A/zh active Pending
- 2009-08-25 US US13/060,406 patent/US20110147341A1/en not_active Abandoned
- 2009-08-25 KR KR1020117003351A patent/KR101282177B1/ko active IP Right Grant
- 2009-08-25 JP JP2010528706A patent/JP5523325B2/ja active Active
- 2009-08-25 WO PCT/JP2009/065136 patent/WO2010029867A1/ja active Application Filing
- 2009-08-27 TW TW098128864A patent/TWI460310B/zh active
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JPH06310492A (ja) * | 1993-04-23 | 1994-11-04 | Fuji Xerox Co Ltd | チタン系薄膜のエッチング液及び半導体装置の製造方法 |
JP2005146358A (ja) * | 2003-11-17 | 2005-06-09 | Mitsubishi Gas Chem Co Inc | チタンまたはチタン合金のエッチング液 |
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KR20110031233A (ko) | 2011-03-24 |
CN102149851A (zh) | 2011-08-10 |
EP2322692B1 (en) | 2016-10-12 |
US20110147341A1 (en) | 2011-06-23 |
JP5523325B2 (ja) | 2014-06-18 |
JPWO2010029867A1 (ja) | 2012-02-02 |
WO2010029867A1 (ja) | 2010-03-18 |
EP2322692A1 (en) | 2011-05-18 |
EP2322692A4 (en) | 2015-05-06 |
TW201014927A (en) | 2010-04-16 |
KR101282177B1 (ko) | 2013-07-04 |
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